ELSEVIER Surface and Coatin_psTechnology 94-95 (1997) IL6

Clean diffusion coatings by chemical vapor deposition

Abstract

An experimental program was undertaken to identify diffusion coating impurities introduced by standard aluminizing processes and to
evaluate the impact of those impurities on oxidation resistance of the resultant Pt aluminide coating. IN-738 tabs and foils were platinum-
electroplated, and then aluminized using three different processes: high-activity pack cementation,high-activity CVD and low-activily
CVD. The results suggest that aluminizing processes which involve aluminum bearing alloys in the coating retort with H2 or H1/HC1 gas at
high temperaturecan contaminatethe diffusion coatingduring deposition.CVD low-activity aluminizing(coatinggasgeneratedat low
temperature outside the coating chamber from 99.999% Al) did not introduce any coating impurities. In addition, the data indicates that
harmful impurities from the IN-738 substrate (sulfur. boron and tungsten) and the electroplating process (phosphorus) were removed from
the coating during deposition. The CVD low-activity Pt aluminide coatin, 0 wasthe ‘cleanest’in the study,and it exhibitedthe besthigh-
temperature oxidation resistance of the coatings considered. It can be concluded that trace elements in diffusion coatings from the
superalloy substrate and/or the aluminizing process can adversely effect the oxidation resistance of those coatings, and rhat CVD low-
activity aluminizing yields cleaner coatings than other commercially available aluminizing techniques. 0 1997ElsevierScienceS.A.

Kry~r~oviis: Diffusion coatings; Impurities; Chemical vapor deposition: Aluminizing

1. Introduction impurities introduced by commercial aluminizing pro-

At temperatures greater than about 1273 K, high-tem-
perature oxidation is the most important form of environ-
mental attack observed in the hot section of gas turbine
engines.High-temperature oxidation of an aluminide coat-
ing is a chemical reaction whoserate controlling processis
the diffusion of reactants (both oxygen inward and alumi-
num outward [ 11)through an aluminum oxide product layer.
Coatings which form adherent and slow growing ahunina
(A1,03) scales(high purity coatings) are the most likely to
provide adequate resistanceto oxidation. Specifically, the
dissolution of solutesfrom the substrate(especially refrac-
tory elements)into the aluminide coating and consequently
the alumina scalecan result in doping [2,3] effects; that is,
they can significantly increasethe growth rate of the oxide
scale. In addition, the presence of surface active tramp
impurities (such as sulfur) in the aluminide coating can
have a detrimental effect on the adherence [4] of the pro-
tective oxide scale.
The goal of this study was to identify diffusi~l coating
* Correspondiq author. Tel.: +l 616 8947396; fax: +l 616 5947400
cesses,and to evaluate the impact of those impurities on
the coatings’ oxidation resistance.The subsequentdescrip-
tion of this researchprogram will begin with an outline of
the experimental procedure, followed by a summary of the
experimental results. The data and possibleinterpretations
will be discussednext, and finally, conclusionswhich can be
drawn from the work will be highlighted.
2. Experimental procedure
An experimental approachwhich can achieve the goalsof
this researchprogram is outlined in this section. The sam-
ples and their preparation are discussedfirst, followed by a
summary of the testsperformed and the information sought
from them.
Samplesfor this study were conventional. vacuum cast
IN-738 tabs (2.5 x IO-’ M x 1.25 x lo-’ M x 0.3 x lo-’
M) and foils (2.5 x lo-’ M x 1.25 x lo-’ M x 150-
200 x 1-Q-fM) made from the samealloy masterheat. The
tabs and foils were platinum electroplated using a bath
based upon a hydrogen phosphate buffer solution [5].
Next, the samples were divided into three groups, and

0257~8972197/$17.00 0 1997 Elsevier Science S.A. All rights reserved

PII SO25?-8972(97)00467-2
2 B.M. Wumes, D.C. Punola / Surfuce
Pack Cementation Process
STEEL
Parts are located in powder within retort.
TYPICAL PACK POWDER MIXTURE
a) 33% Metal Powder
b) Balance Oxide Powder
Fig. 1. Schemalic diagram of pack cementation aluminizing process.
then each group was aluminized using one of three pro-
cesses: high Al activity pack cementation (LDC-2E), high
Al activity CVD (MDC-150) and low Al activity CVD
(MDC-ISOL). In the high-activity pack cementation process
(see Fig. l), the component was packed in a Cr-Al Alloy/
A&O3 powder mixture contained in a steel retort. The pack
cementation process was not halide salt activated and was
conducted in a hydrogen atmosphere. The two CVD pro-
cesses utilized aluminum trichloride gas generated at low
temperature (T < 600 K) from 99.999 wt.% Al metal, out-
side the coating retort. In the low-activity CVD aluminizing
process (see Fig. 2), the internal and the external surfaces of
the component are supplied coating gas by separate AlCls
generator circuits. The high-activity aluminizing process
(see Fig. 3) involves only one change from the low-activity
process. The external coating gas is produced using low and
high-temperature aluminum chloride generators in series.
The high-temperature aluminum subchloride generator
forms an annulus centered on the retorts’ axial supply
line, and it contains Cr-Al alloy chunks. One, potentially
important, difference between the low-activity CVD pro-
cess and the two high-activity ones is that the two high-
activity processes involve high-temperature aluminum
sources (possible source of coating impurities).
Following coating application, all samples received the
standard post aluminizing heat treatments for IN-738 (2 h at
1394 K, rapid cooling and 24 h at 1116 K). Representative
foil samples were set aside after each step in the processing
to be used for subsequent bulk chemical analysis. Oxidation
test tabs in both the as coated, and the coated plus heat
treated conditions were reserved for metallographic pre-
paration and microscopic examination.
Three types of tests were used in this program: bulk che-
mical analysis of foils, electron microprobe chemical ana-
lysis on metallographically prepared cross sections of both
tabs and foils, and cyclic oxidation testing of coated tabs.
and Coatings Technology 94-95 (1997) 1-6
The bulk chemical composition of superalloy foils after
various stages in processing was determined using the fol-
lowing techniques: (a) carbon and sulfur concentrations
were measured with a Leco CS444LS (b) major metal (P,
W, B etc.) concentrations were determined with a Jarrell
direct read emission spectrometer, and (c) the tramp metal
impurity (Pb, Bi, Se etc.) concentrations were established
using a Perkin Elmer 5000 atomic absorption spectrometer.
The chemical composition of coatings was also determined
using wave length dispersive X-ray spectroscopy on a
Comeca microprobe. Average coating compositions were
obtained from ten large rasters across the coatings, and
composition gradients were investigated by point profile
analysis.
Test tabs coated along with the foils were used for cyclic
oxidation testing at 1373 K. Each l-h test cycle included 50
min at temperature and 10 min cooling to room temperature,
Samples were weighed to the nearest 0.1 mg before the test
and after each 50-cycle test interval. Failure was defined as
zero crossover; that is, when the sample weight after a test
interval was less than or equal to the initial weight. For each
coating type, five samples were tested to failure, then the
cycles to failure were averaged. The average number of
cycles to failure were subsequently normalized to account
for differences in coating thickness. The reported coating
thicknesses were derived by averaging ten measurements
taken at 500x magnification with a light microscope on
polished cross-sections of heat-treated samples.
These experiments permit examination of the transport of
potentially harmful elements to and away from a superalloy
substrate during state-of-the-art aluminizing processes. In
addition, these tests facilitate evaluation of the relationship
between a diffusion coating’s ‘cleanliness’ and its oxidation
resistance.
Low Activity Aluminizing
Chemical Vapor Deposition
INTERNAL
MASS
FLOW
IER
CONTRC
i
SOURCE
GASES
Fig. 2. Schematic diagram of the CVD low-activity aluminizing apparatus.
 B.M. Warms, D.C. Punola / Swjace and Coatings Technology 94-95 (1997) 1-6 3

Table 1
Bulk chemical analysis of IN-738 foils
MDC-150L on IN-738 Foil
Element Pt-plated LDC-ZE- MDC-I50- MDC-150L-
Coated Coated Coated

B 0.012% 0.014% 0.015% 0.005%

P 0.045% 0.044% 0.039% 0.014%
S 6 mm 7 Pwm 8 wm 5 ppm
w 2.39% 2.3% 0.57% 0.13%

All concentrations by weight.

3. Results

In the following paragraphs, selected results from the

experimental program are summarized. The data presented
here are only intended to illustrate the most enlightening
phenomena, not to give a comprehensive report on the
research program. The bulk chemical analysis results on 0 10 20 30 40 50 60 70 80 90 160 rio 150 li0
Distance (microns)
four elements (S, P, B and W) will be shown first, followed
by information from the optical and electron microscope
Fig. 4. Microprobe point profile analysis across MDC-15OL coating on IN-
examinations of metallographically prepared cross-sections
738 foil.
of both tabs and foils. Finally, the cyclic oxidation data of
the various coatings is reviewed.
substrate (W, S, P and B). A comparison of the concentra-
3.1. Chemical analysis of foils tions of these elements in the as-plated and the three differ-
ent as-coated conditions reveals some interesting facts. First
Bulk chemical analysis of superalloy foils both before and foremost, the CVD low-activity aluminizing process
and after aluminizing was conducted, and the results for reduced the bulk concentration of each of these elements
sulfur, phosphorus, boron and tungsten are presented in in the superalloy foils. Second, the presence of an aluminum
Table 1. These elements were selected for discussion chromium alloy (22 ppmw S and 0.031 wt.% B) in the coat-
because they can be introduced in diffusion coatings by ing retort at high temperature results in the transport of
three different sources: (1) the aluminizing process (S and impurities (sulfur and boron) to the coating during deposi-
B), (2) the Pt plating process (P) and (3) the superalloy tion.
The purification effect of the CVD AlCls-based aluminiz-
High Activity Aluminizing ing process is also indicated by the microprobe composition
profiles across the MDC-ISOL coated foil shown in Fig. 4,
Chemical Vapor Deposition As can be seen, the concentrations of S, P, B and W decrease
INTERNAL continuously from a maximum in the diffusion zone to mini-
TO
METAL HALIDE ATMOSPHERE mum values (significantly below those in the alloy) at the
GENERATOR external surface. Concentration gradients of this type are

T
EXTERNAL
typical of gas-solid reactions where solute elements are
being removed from the external surface of the solid by
chemical reaction with the gas phase [6]. It should be
noted, the structure and composition gradients are sym-
ER metric about a plane through the midthickness of the foil,
so only one half of the profile is shown. Also, the concen-
tration profiles have been smoothed for clarity, and the X-
PUMP
ray counts for each element have been normalized to the
maximum value in the sample so all the data could be shown
ALUMINUM on one graph.
ALLOY
SOUkE CHIPS
GASES 3.2. Metallographic examination of coated tabs

The following paragraphs summarize the results of the

Fig. 3. Schematic diagram of the CVD high-activity aluminizing appara- optical and electron microscope examinations of metallo-
tus. graphically prepared cross-sections of the coatings in both
 LDC-2E on IN-738 Tabs MDC-150L on IN-738 Tabs
AS COATED AS COATED AS COATED AS COATED
AND SOLUTION HEAT TREATED AND SOLUTION HEAT TREATED

THICKNESS = 49 pm THICKNESS = 74.3 pm THICKNESS = 78.3 pm THICKNESS = 77.5 pm

AVERAGE COMPOSITION AVERAGE COMPOSITION AVERAGE COMPOSITION AVERAGE COMPOSITION
35.5 wt% Pt 30.6 wt% Pt 21.6 wt% Pt 19!at%Pt
25.6 wt% Al 19.96 wt% Al 24.1 wt% Al 19.5 wt% Al
(24 GW Ma) W

Fig. 5. Baclocattcr electron images, average compositions and thisknrsscs Fig. 7. Backscatter electron images, average compositions and thicknesses
of LDC-2E on IN-738 tabs in the as-coated (?a) plus the as-coated and of MDC-ISOL on IN-738 tabs in the as-coated (4a) plus the as-coated and
heat-treatsd (?b) conditions. heat-treated (4b) conditions.

the as-deposited,and the as-depositedplus heat treatedcon- high Al activity, inward-grown platinum aluminide coat-
ditions. ings. In contrast, the MDC-15OL coating had a single-
In the us-coatedcondition, both LDC-2E and MDC-150 phase(Ni,Pt)Al additive layer, and about one-third of the
had a two-phase((Ni,Pt)Ai plus PtAl?) outer layer (seeFigs. thicknesswasthe diffusion zone (seeFig. 7). A well devel-
5 and 6) on top of an (Ni,Pt)Al layer and finally a thin oped diffusion zone is characteristic of a growth process
diffusion zone. This btructura is typical of as-deposited, dominated by the outward transport of nickel. The coating
thicknessesin the as depositedcondition appearin Table 2
MDC-150 on IN-738 Tabs and Figs. 5-7.
AS COATED AS COATED After the post-aluminizing heat treatment, both of the
AND SOLUTION HEAT TREATED two-phase coatings exhibited significant changesin struc-
ture, composition and thickness, while the MDC-150L was
relatively unaffected. Specifically, the high-activity two-
phasecoatings transformed to a single-phasestructure dur-
ing the heat treatment (seeFigs. 5 and 6), and the thick-
nesses(seeTable 2) increasedapproximately 52% and 67%
for LDC-2E and MDC-150, respectively. The change in
both the platinum and the aluminum concentrations (see

Table 2
Microprobe analysis and thickness of coated IN-738 tabs
LDC-2E MDC- 150 MDC-15OL
As-coated
Thickness 49j4m 52.8 pm 78.3 pm
THICKNESS = 52.8 pm THICKNESS = 88 pm [All 25.6wt.% 31.3 wt.% 24.1 wt.%
AVERAGE COMPOSITION AVERAGE COMPOSITION ml 35.5 wt.% 29.9 wt.% 21.6 wt.%
29.9 wt% Pt 22.6 ‘#it% Pt
31.3 wt% Al 23.2 WY./. Al As-coated and heat-treated
Pa) W Thickness 71.3 flrn 88 pm 77.5 pm
[AlI 19.96 wt.% 23.2 w.% 19.5 Wt.%
Fig. 6. Backsxtter electron images, average compositions and thicknesses [Ptl 30.6 wt.9 22.6 wt.% 19 wt.%
of MDC-150 on IN-738 kabs in the as-coated (33) plu5 the as-coated and
heat-treated (3b) condition>. Thickness equals coating and diffusion zone.
 B.M. Wanes, D.C. Pmola / Sqtace aX%ontings Techwlogy 91-95 (1997) 1-6

1373K Cyclic Oxidation
Pt Alutninides On IN-738
6007 * Failure Zero Cross
2 be on possibleimpurity transport processesduring aluminiz-
‘Z 500
s
r 1 403 cvcles _418 cycles
- ~
4. Discussion
The experimental program yielded some interesting
results, and plausible explanations for these observations
Over l
564 cycles
are discussedin the following paragraphs.The focus will
ing and the relationship between clean aluminizing and the
oxidation resistanceof coatings.
The chemical analysis of coated samplesindicates that
the transport of potentially harmful impurities is possible
during aluminizing. One mechanismfor impurity transfer
is by reaction with the coating gas.
Sulfur can react with hydrogen in either the pack or the
CVD processesto form hydrogen sulfide gas. In the high-
activity aluminizing processes(pack or CVD), the alumi-
num source(Al-Cr alloy) contained a higher sulfur concen-
tration (22 ppmw S) than the substrate ([S] = 5 ppmw).
- I

LDC-SE MDC-1% MDC-1501
Fig. 8. Normaiized cyclic oxidation life of various platinum aluminide
coatings on TN-738 tabs in 1373 K testing.
Table 2) of the inward-grown coatings during the thermal
cycle was alsosignificant, and ranged from 4.6 to 8.1 wt.%.
It should be noted that the observed metamorphosesof the
two-phase coatings during the post-coat heat treatment is
similar to the changes encountered during engine testing
at both G.E. [7,8] and Rolls-Royce [9]. The changes in
MDC-15OL following the heat treatment were minor in
comparisonwith those for the high-activity platinum alumi-
nides. The composition variations (seeTable 2) for Pt and
Al ranged from 2.6 wt.% to 4.6 wt.% (about one-half that for
high-activity coatings), and the thickness changed by only
1% (insignificant compared with the inward-grown coat-
ings).
3.3. Oxidation testing of coated tabs
The resultsof the cyclic oxidation testing are summarized
in Fig. 8. A comparisonof the normalized test resultsfor the
three platinum-modified aluminide coatings showsthat the
MDC-15OL (the outward-grown CVD coating) had about
40% longer life than LDC-2E and about a 35% life improve-
ment compared with MDC-1.50.
The important experimental resultscan be summarizedas
follows. The bulk chemical analysis of the foils indicated
that impurities can be transported both toward and away
from a substrate during standard aluminizing processes,
and that only low-activity CVD aluminizing purifies the
coating during deposition. The microscopic examination
demonstrated that the high-activity coatings are unstable
as deposited,exhibiting significant growth and composition
changesupon heat treatment. Finally, cyclic oxidation test-
ing of the three single-phase(two inward-grown and one
outward-grown) platinum-modified aluminide coatings
shows that low-activity CVD ahnninizing produces the
best oxidation resistance.
Consequently, sulfur (as HzS) was transported from the
high-temperature aluminum source to the coating. The gas
phaseprocessproducesmore sulfur transport (seeTable 1)
to the substratethan rhe pack process,and this fact provides
additional support for the proposed mechanism. In low-
activity CVD aluminizing, the superalloy substrateappar-
ently had the highest sulfur concentration, since S was
removed from the coating surface during aluminizing.
Transport of W (from the substrate), P (from Pt electro-
plating and the substrate)and B (from either the substrateor
the high-temperatureAl source)may involve chlorination of
theseelementsand the subsequentevaporation of the chlor-
ides. In an unactivated pack, the changein the tungsten and
phosphorusconcentrations is insignificant compared with
the H2/HCl/Al,C1, gas mixtures in CVD (see Table l), as
would be expected if chlorination of those elements and
evaporation of the chlorides is the correct transport process.
This mechanismmay also produce impurity transport both
to and away from the coatings during deposition, as sug-
gested by changesin the bulk boron concentrations pro-
duced by the high-activity (increased[B]) and low-activity
(decreased[B]) CVD processes.
The high-temperaturealuminum source(the Al-Cr alloy)
contained a higher concentration of boron than the IN-738
substrate.Therefore, transport of B from the Al sourceto the
coating is thermodynamically possible,and was observedin
both the pack and CVD high-activity processes.The trans-
port mechanismof B in the unactivated pack cementation
processremains unclear, but it may be related to diffusion
between the substrateand the pack powder in contact with
it.
The resultsof the cyclic oxidation testsindicate that low-
activity CVD aluminizing produces superior oxidation
resistance compared with the high-acti\jity processes.
Since the low-activity processalso purifies the coating dur-
ing deposition, this result suggeststhe oxidation resistance
and the purity of the (Ni,Pt)Al are related.
The removal of impurities from the coating by reactions
with hydrogen or hydrogen chloride gasin the low-activity
6 B.M. Wurnes, D.C. P~moia / Su$~tce and Coutings Technology 94-95 (1997) 1-6
CVD process produces a ‘clean’ (Ni,Pt)Al additive layer.
Furthermore, it has been suggested [IO] that platinum dis-
solved in nickel aluminide can inhibit the outward diffusion
of impurities from the substrate into the coating, and this
effect might help maintain the improved purity of the coat-
ing during testing or engine service. Higher purity (Ni,Pt)Al
coatings may form a ‘cleaner’ alumina scale (slower grow-
ing [2,3]) that is more adherent [4], and consequently, they
exhibit superior oxidation resistance.
5. Conclusions
The results of this research and information available in
&heopen literature permit several conclusions to be drawn in
relation to impurity transport during standard aluminizing
processes and its impact on oxidation resistance. The fol-
lowing statements summarize several of these conclusions.
The transport of impurities to or away from coatings
during standard aluminizing processes is possible.
Gas-solid reactions are the primary mechanisms of
impurity transfer in the processes considered.
High-temperature aluminum sources inside the coating
chamber are also a significant source of coating impu-
rities during aluminizing.
CVD low-activity aluminizing purifies the (Ni,Pt)Al
additive layer during growth.
The purity of (Ni,Pt)Al is directly related to its oxidation
resistance.
The implications of these conclusions are clear. As the
inlet temperatures of gas turbine engines increase, protec-
tive coatings will be required to exhibit continuous
improvemenb in oxidation resistance. Clean aluminizing
may be a requirement to achieve this performance goal in
diffusion coatings. The results also suggest other processes
in the production of platinum-modified diffusion coatings
should be examined for possible transport of harmful impu-
rities to the coating. In particular, commercially utilized
platinum electroplating baths contain high concentrations
of undesirable elements which may be deposited with the
platinum, and which may adversely effect the oxidation
resistance of the product coating. Finally, clean over-alumi-
nizing of MCrAlY type overlay coatings may also be ben-
eficial to those products.
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